INDICATORS FOR AIR POLLUTANTS AND CLIMATE CHANGE: …

Cristina SabbioniInstitute of Atmospheric Sciences and Climate (ISAC)

National Research Council (CNR), Italy

International Conference New Indicators for a Better World

Ravenna, 26 September 2013

INDICATORS FOR AIR POLLUTANTS AND CLIMATE CHANGE: IMPACT ON

CULTURAL HERITAGE

ENVIRONMENT – CULTURAL HERITAGE

-Stone/Masonry Materials:MarbleLimestoneSandstoneBricksClay containing mat.

- Wood- Metals

IronBronzeCopperLeadZinc

- Glass

MATERIALS

- Temperature- Relative Humidity - Precipitation - Wind- Gas (SO2 , NOx)- Particles - Sea salts- pH precipitation

CLIMATE/POLLUTIONPARAMETERS

INTERACTION

COMBINATION

ACCUMULATION

C. Sabbioni, ISAC-CNR, Bologna, Italy Ravenna , 26 September 2013

IMPACT ON CULTURAL HERITAGEIMPACT ON CULTURAL HERITAGE

• Damage layer and black crust formation

• Chemical dissolution (surface recession)

• Salt crystallisation (decohesion, powdering)


BLACK AREAS

Environment - Cultural Heritage interactionMarble/limestone in urban areas

WHITE AREAS- Rainwashed areas - Chemical dissolution- Material loss

- Rain sheltered areas- Calcite gypsum (Sulphation

process - SO2)

- Carbonaceous particle deposition

BLACK CRUSTS

SURFACE RECESSIONC. Sabbioni, ISAC-CNR, Bologna, Italy Ravenna , 26 September 2013

SULPHATIONgypsum (CaSO4•2H2O)

SULPHATIONgypsum (CaSO4•2H2O)

Carbonaceous particles

BLACK CRUSTS FORMATION AND SOILING

BLACK CRUSTSBLACK CRUSTS


1

10

100

1000

10000

100000

1000000

SO4--

SO3--

NO3-

NO2-HPO4-

- F-

Cl- Br -CHO2-

C2H3O

2-C2O

4--

Con

cent

ratio

n (p

pm)

MILAN

FLORENCE

ROME

VENICE

PARIS

SEVILLE

LONDON

SOLUBLE ANION CONCENTRATION ( µµµµg/g), IC

SO2 dry deposition

Bonazza et al., Atmos. Env. (2005)


FUTURE SCENARIO OF SO2FUTURE SCENARIO OF SO2NOAHs ARK SSPI-CT-2003-501837

Shift in modern urban atmospheres from a SO2 dominated situation to a multipollutant situation

Joakim Langner

SULPHATION PROCESS DECREASE SULPHATION PROCESS DECREASE C. Sabbioni, ISAC-CNR, Bologna, Italy Ravenna , 26 September 2013

TC = CC + EC + OCTC = CC + EC + OC

Stone substrate

Stone substrate

NCCNCC

�Atmospheric deposition�Biological weathering�Surface treatments

�Atmospheric deposition�Biological weathering�Surface treatments

Particles emitted by combustion processesParticles emitted by combustion processes

CARBON IN THE CARBON IN THE

BLACK CRUSTS/DAMAGE LAYERS

Ghedini et al., EST (2006)

CARAMEL EVK4-CT-2000-00029

Fixed and mobile combustion sources


CRUSTS European Monuments(carbonate stone)

0%

10%

20%

30%

40%

50%

60%

70%

80%

90%

100%

FLORENCE ROME PARIS SEVILLE LONDON

OC (%)

EC (%)

OC prevails on

monuments in

European towns

due to

urban traffic

Bonazza et al. Atmos. Env. (2005)


Modern crusts are richer in organic compounds

SITE MONUMENT AGE (years) EC (%) OC (%) EC/OCMILAN CATHEDRAL 500 1,73 0,70 2,48MILAN CATHEDRAL 500 1,17 0,53 2,20MILAN CATHEDRAL 500 1,70 0,62 2,75

VENICE CORNER PALACE 500 1,52 0,71 2,16VENICE CORNER PALACE 500 0,78 0,67 1,17ROME VITTORIANO 100 1,34 1,62 0,83ROME VITTORIANO 100 0,93 1,16 0,80

RAVENNA P. RASPONI 100 0,88 1,67 0,53FLORENCE S.M. DEL FIORE 50 0,66 1,11 0,59

MILAN CATHEDRALOLD-MODERN CRUSTS

VITTORIANO MONUMENT, ROME


St. Maria del Fiore, Florence

1954-1955

Not surveyed

Lucia De Prato


2010

Not surveyed

AESTHETIC IMPACT ON SURFACE BUILDINGSAESTHETIC IMPACT ON SURFACE BUILDINGS• Modern urban atmospheres deposit

– less sulphur (phytotoxic)– more nitrate (nutrient)– more organic (nutrient)

• Surface yellowing• Warmer conditions• Encourage biological damage

(green, grey and black)

Grossi et al., 2006; Bonazza et al., 2007; Grossi et al., 2008, Smith et al., 2010


-1

-0,5

0

0,5

1

1,5

2m

ean

a*

-2

0

2

4

6

8

10

12

mea

n b

*

Increase a*: more redIncrease b* : more yellow

Florence

Reference marble

Black crusts / damage layers

AESTHETIC IMPACT ON SURFACE BUILDINGSAESTHETIC IMPACT ON SURFACE BUILDINGS

C. Sabbioni, ISAC-CNR, Bologna, Italy

EC Project TeachRavenna , 26 September 2013

O

T-SE

RC-B

COLOUR vsDIRTINESS

COLOUR vsDIRTINESS

Impossibile v isualizzare l'immagine.




Ravenna , 26 September 2013C. Sabbioni, ISAC-CNR, Bologna, Italy



RC-B

SETTING LIMITS FOR SOILINGSETTING LIMITS FOR SOILING

INCREASING CARBON LOADOR INCREASING POLLUTION

Acceptable complaint?

EC = 2-3 ug/m3

Ravenna , 26 September 2013C. Sabbioni, ISAC-CNR, Bologna, Italy




Centennial Hall, Poland

Pollution impact on modern cement built heritage


Reactivity to SO 2Reactivity to SO 2Impossibile v isualizzare l'immagine.

Vulnerability of building materials is different depending on chemical composition and porosity

SIMULATION CHAMBER TEST





Atm

osph

ere

Cem

ent

Mor

tar

SO2gas


SO4=

SO3=SO3= SO4

=SO4=


Catalysts aerosol


Catalysts material

CALCIUM CARBONATECALCIUM CARBONATE

Gypsum formation on cementGypsum formation on cement

GYPSUMGYPSUM

CALCIUM ALUMINATESCALCIUM SILICATES

CALCIUM ALUMINATESCALCIUM SILICATES


SECONDARY DAMAGE PRODUCTSSECONDARY DAMAGE PRODUCTSImpossibile v isualizzare l'immagine.

3CaO·Al2O3·3CaSO4·31H2O3CaO·Al2O3·3CaSO4·31H2O


CaSiO3·CaSO4·CaCO3·15H2OCaSiO3·CaSO4·CaCO3·15H2O

Gypsum + Calcium silicate

THAUMASITE

Gypsum + Calcium aluminate

ETTRINGITE

Sabbioni et al., Atmos. Env. (2001)


C. Sabbioni, ISAC-CNR, Bologna, Italy

ETTRINGITEFORMATION

ETTRINGITEFORMATION

TAUMASITE

FORMATION

TAUMASITE

FORMATION


Impossibile v isualizzare l'immagine.Impossibile v isualizzare l'immagine.

10-15 nm

EC Project EDAMM

Laboratory test

Damage occurs in spite of SO2

decreases

BREAKDOWN BY EXPANSIONBREAKDOWN BY EXPANSION

ETTRINGITE DISSOLUTION /DECOMPOSITION

ETTRINGITE DISSOLUTION /DECOMPOSITION

Ravenna , 26 September 2013


CLIMATE CHANGE: WATER CYCLEImpossibile v isualizzare l'immagine.

Yearly precipitation 2070-2099

Structural damageErosionDissolutionSwelling-shrinkageFrost damageSalt crystallizationBiodeterioration

Major cause of deterioration (XXI century)




Relative humidity cycles =75.5%(Salt crystallisation)


2070-2099


Brick Masonry


Salt crystallisationSalt crystallisationImpossibile v isualizzare l'immagine. Impossibile v isualizzare l'immagine.

Increase

Decrease

.…general increase.........Western Europe. Temperate fully humid climates: highest potential for salt damageand possible higher number of transitions in summer. Climates with dry summers:lesser frequency of transitions in summer (Grossi et al., 2011)


Biomass Accumulation on MonumentsImpossibile v isualizzare l'immagine.

Linked to temperature and precipitation



2070-2099


Biomass Accumulation on Monuments

Linked to temperature and precipitationProjections valid for rural areas





““““Gutta cavat lapidemGutta cavat lapidemGutta cavat lapidemGutta cavat lapidem””””


Dry depositionImpossibile v isualizzare l'immagine.


Acid Rain

















HNO3

H2SO4 NOx

SO2

Material dissolution due to the chemical attack induced by:

1. Clean rain (rain at pH 5.6 in equilibrium with 330 ppm CO 2 –karst effect)

2. Acid Rain (additional acidity due to anionic components, such as SO4

2-, NO3-……)

3. Dry deposition (gaseous pollutants occurring between precipitation events)

SURFACE RECESSION OF CARBONATE STONES

Material surface erosion due to the mechanical effect of rain

+


Lv was recalculated on a daily basis correcting for th e predicted temperature and the CO 2 increase from 330 in 1961 to 750 ppm in 2099 as suggested under A2 emission scenarios : L v ranges from 18.8 and 21.8 µm/m

L = 18.8 · R

SIMPLIFIED LIPFERT FUNCTION

Lv need to be corrected for future scenarios:

RAIN : PRECIPITATION NOT INCLUDING SNOW

Lv intercept term based on the solubility of CaCO 3 in equilibrium with 330 ppm CO 2 (µm/m) at 20 °°°°C

Lv intercept term based on the solubility of CaCO 3 in equilibrium with 330 ppm CO 2 (µm/m) at 20 °°°°C



Sur

face

rece

ssio

n (µ

m/y

ear)

Lipfert function assumes that precipitation arrives only in liquid phase. The snow effect has been taken into account by allowing no recession for days with daily mean temperature less than 0 °°°°C.

CORRECTION FOR SNOW EFFECT

CO2 andsnow

corrections are

necessary for

evaluating the future change




MAPPING SURFACE RECESSION

1961-1990

2070-2099Central Europe, UK, Iceland, Sandinavian Peninsula and

the northern Spain will experience the

highestsurface recession

(20-30 µm/year)

Absolute values of surface recession

General model HadCM3

C. Sabbioni, ISAC-CNR, Bologna, Italy Ravenna , 26 September 2013Ravenna , 26 September 2013






30% increase

1961-1990

2070-2099




Surface recession is expected to be higher in the areas thatwill be more affected by precipitation, that are the mountai nchains (Alps, Carpathians, Pyrenees) and the westerliesexposed areas, reaching values higher than 30 µm/year

2070-2099

Bonazza et al. Science of the Total Environment 20 09


Impossibile v isualizzare l'immagine.Impossibile v isualizzare l'immagine.


The Mediterranean Basin in general will continue to experience the highest level of risk.

In the near and far future thermal stress will thre aten more and more Central Europe.

THERMAL STRESS



C. Sabbioni, ISAC-CNR, Bologna, Italy Limassol (Cyprus) , 1 November 2012Ravenna , 26 September 2013

GUIDELINES FOR THE PREVENTIVE CONSERVATION OF MONUMENTS LOCATED IN URBAN AREAS

- Identify and prioritize climate parameters and pollutants causingdeterioration , depending also on the sensitivity of materials and theenvironmental context in which monuments are located.

- Define risks of cultural heritage by adopting continuousenvironmental monitoring close to monuments as a valuable tool.Definition of risks allows heritage managers to single out t he prioritiesfor greater investment in preservation and funding of actio ns to reducethe cause.

- Promote actions aimed at reducing exposure of cultural heritage toharmful agents

- Mitigate the negative causes by regulation at regional and local levelsaimed at the reduction of pollutants, especially in developing urbanplans for a sustainable mobility.



THANKSAlessandra BonazzaAdriana BernardiFrancesca BecheriniNadia GhediniPaola De NuntiisIzabela Joanna OzgaIrene NataliChiara BertolinValentina Turci Paolo MandrioliDario CamuffoFrancesca TittarelliOrlando Favoni


INDICATORS FOR AIR POLLUTANTS AND CLIMATE CHANGE: …

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